1. Field of the Invention
The present invention relates to a resin composition comprising ethylene-based polymers excellent in environmental stress cracking resistance (hereinafter referred to as ESCR) and stiffness without imperfections or gel, excellent in moldability, and suitable for blow molding to produce e.g. cans and bottles, and for extrusion molding to produce pipes, and a process for its production.
2. Discussion of Background
In recent years, higher performance has become required for polyethylene as its application and demand increases. For example, physical properties required for polyethylene for blow molding or for extrusion molding may be good ESCR, high stiffness due to high density, good moldability, etc.
Generally speaking, the polyethylene having lower density, or higher intrinsic viscosity and higher molecular weight leads better ESCR property of the resin composition. However, when the value of polymer density is lowered, the mechanical strength of the composition is lowered as well as stiffness. When the polyethylene has high value of intrinsic viscosity or high molecular weight, the composition is poorly flowable to cause the problem of molding. Thus, improving ESCR of the resin composition in control of the density of the polymers and increasing the stiffness of resin composition, are against each other. Likewise, improving ESCR of the composition in control of the molecular weight of the polymers and improving the moldability of the composition, are against each other.
Heretofore, as a method of producing a polyethylene having a broad molecular weight distribution to be used for blow molding, a method of producing a polyethylene having a high molecular weight and a polyethylene having a low molecular weight in more than two consecutive polymerization steps has been considered, and various methods have been proposed as multi-step polymerization methods. Generally speaking, a polyethylene obtained by a two-step polymerization method is excellent in the balance of stiffness and ESCR, as compared with a polyethylene obtained by a single step polymerization method. For example, according to the method described in JP-A-64-79204 or JP-A-2-155906, it is disclosed that an xcex1-olefin is copolymerized in order to control the stiffness of the polyethylene, and the balance between the stiffness and environmental stress cracking resistance (ESCR) can be remarkably improved by incorporating the xcex1-olefin so that the content of the xcex1-olefin in the higher molecular weight polymer is higher than the content of the xcex1-olefin in the lower molecular weight polymer.
However, the product obtained by such a two-step polymerization method has disadvantages that generally, the bonding strength at a pinch-off portion of the blow molded articles is small, and the swelling ratio is small. As a means to overcome such disadvantages of the two-step polymerization method, a three-step polymerization method has been proposed in, for example, JP-A-58-138719, JP-A-59-227913, JP-A-64-79204, JP-B-59-10724, JP-B-62-61057, JP-B-3-29805 and JP-B-4-14686. In the method described in these publications, three components having different molecular weights are produced in each step. However, as pointed out in JP-B-4-14686, there is a problem that the balance of stiffness and ESCR tends to be poor, although the swelling ratio of the obtained polyethylene can be improved. Further, in the three-step polymerization method as proposed by such prior art, generally in addition to the lower molecular weight component and the high molecular weight component produced by normal two-step polymerization, a small amount of an ultrahigh molecular weight component is produced as a third component, and consequently, a polyethylene containing a small amount of a polymer having such a very high molecular weight tends to form imperfections or gel.
Therefore, it is an object of the present invention to provide a resin composition comprising ethylene-based polymers excellent in ESCR and stiffness without imperfections or gel, and excellent in moldability, and a process for producing such a resin composition.
The present inventors have conducted extensive studies to solve the above-mentioned difficult problems and establish a resin composition comprising ethylene-based polymers suitable for blow molding or extrusion molding, and a process for its production, and, as a result, have found that by combining three types of polymers having specific structures which are not ultrahigh molecular weight components, at specific contents, and further by setting the difference in molecular weight (evaluated by an intrinsic viscosity) between component (B) and component (C) among the three types not to be so large, and differentiating the contents of xcex1-olefins in the two components, all of the above-mentioned requirements can be satisfied and the object of the present invention can be realized. The present invention has been accomplished on the basis of these discoveries.
Thus, the present invention provides a resin composition comprising the following components (A), (B) and (C), wherein the content of component (A) is from 10 to 90 wt %, component (B):component (C)=from 10:1 to 1:5 (weight ratio), the intrinsic viscosity [xcex7] is in the range from 0.17 to 0.40 m3/kg, and the density is in the range from 935 to 968 kg/m3:
Component (A): a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.5 wt %, and an intrinsic viscosity [xcex7] of from 0.035 to 0.17 m3/kg,
Component (B): a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.5 wt %, and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg, and
Component (C): a copolymer of ethylene having an xcex1-olefin content of from 0.7 to 15 wt %, and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg.
The present invention also provides a process for producing a resin composition comprising ethylene-based polymers, which comprises carrying out
step (a): a step of producing from 10 to 90 wt %, based on the total amount of polymerized polymers, of a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.5 wt %, and an intrinsic viscosity [xcex7] of from 0.035 to 0.17 m3/kg, at a temperature of from 70 to 110xc2x0 C.,
step (b): a step of producing a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.5 wt %, and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg, at a temperature of from 40 to 90xc2x0 C., and
step (c): a step of producing a copolymer of ethylene having an xcex1-olefin content of from 0.7 to 15 wt %, and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg, at a temperature of from 30 to 80xc2x0 C., in an optional order, by using a catalyst which comprises a solid catalyst component (E) containing at least titanium, magnesium and a halogen, and an organic aluminum compound, wherein the three-step polymerization is carried out so that the ratio of amount of polymerized polymers in steps (b) and (c) becomes step (b):step (c)=from 10:1 to 1:5 (weight ratio), to produce a resin composition having an intrinsic viscosity [xcex7] of from 0.17 to 0.4 m3/kg and a density of from 935 to 968 kg/m3.
The present invention further provides a process for producing a resin composition comprising ethylene-based polymers, which comprises carrying out
step (a): a step of producing from 10 to 90 wt %, based on the total amount of polymerized polymers, of a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.5 wt %, and an intrinsic viscosity [xcex7] of from 0.035 to 0.17 m3/kg, at a temperature of from 70 to 100xc2x0 C.,
step (b): a step of producing a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.5 wt %, and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg, at a temperature of from 40 to 90xc2x0 C.,
step (c): a step of producing a copolymer of ethylene having an xcex1-olefin content of from 0.7 to 15 wt %, and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg, at a temperature of from 30 to 80xc2x0 C., in an optional order, by using a catalyst which comprises a solid catalyst component (F) containing a metallocene compound and an aluminoxane, and an organic aluminum compound, wherein the three-step polymerization is carried out so that the ratio of amount of polymerized polymers in steps (b) and (c) becomes step (b):step (c)=from 10:1 to 1:5 (weight ratio), to produce a resin composition having an intrinsic viscosity [xcex7] of from 0.17 to 0.4 m3/kg and a density of from 935 to 968 kg/m3.
Now, the present invention will be described in detail with reference to the preferred embodiments.
The xcex1-olefin as a comonomer for the copolymer of ethylene constituting the resin composition comprising ethylene-based polymers of the present invention, means an xcex1-olefin other than ethylene. As such an xcex1-olefin, one having from 4 to 20 carbons is preferably used. Particularly, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene or 1-icocene, may, for example, be mentioned. Among these, 1-butene, 1-hexene and 1-octene are particularly preferred.
The resin composition comprising ethylene-based polymers of the present invention comprises three components (A), (B) and (C). Among them, component (A) is a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.5 wt % and an intrinsic viscosity [xcex7] of from 0.035 to 0.17 m3/kg. It is preferably a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.3 wt % and an intrinsic viscosity [xcex7] of from 0.04 to 0.15 m3/kg. When the content of the xcex1-olefin in component (A) exceeds 0.5 wt %, the stiffness and ESCR of the resin composition tend to be low. And, when the intrinsic viscosity [xcex7] is less than 0.035 m3/kg, the bonding strength at a pinch-off portion of the blow molded articles tends to be insufficient, and if it exceeds 0.17 m3/kg, ESCR of the composition tends to be low.
Component (B) of the resin composition is a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.5 wt % and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg. Preferably, it is a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.3 wt % and an intrinsic viscosity [xcex7] of from 0.25 to 0.8 m3/kg. In component (B), when the xcex1-olefin content exceeds 0.5 wt %, the stiffness and ESCR of the resin composition tends to be low. Further, when the intrinsic viscosity [xcex7] of component (B) is less than 0.2 m3/kg, the impact resistance of the resin composition tends to be insufficient, and when it exceeds 1.0 m3/kg, the fluidity of the resin composition deteriorates and a gel, imperfections or fish-eyes tend to be formed in the molded articles.
Further, component (C) of the resin composition is a copolymer of ethylene having an xcex1-olefin content of from 0.7 to 1.5 wt % and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg. Preferably, it is an ethylene copolymer having an xcex1-olefin content of from 1.0 to 1.3 wt % and an intrinsic viscosity [xcex7] of from 0.25 to 0.8 m3/kg. In component (C), if the xcex1-olefin content is less than 0.7 wt %, ESCR of the composition tends to be too low, and if it exceeds 15 wt %, the stiffness of the composition deteriorates. Further, when the intrinsic viscosity [xcex7] of component (C) is less than 0.2 m3/kg, the impact resistance of the resin composition tends to be insufficient, and when it exceeds 1.0 m3/kg, the fluidity of the resin composition deteriorates and a gel, imperfections or fish-eyes tend to be formed in the molded articles.
The composition ratio of these three components is such that the content of component (A) is from 10 to 90 wt %, preferably from 30 to 80 wt %, based on the total amount of the composition, and the contents of component (B) and (C) are such that the weight ratio of component (B):component (C) is from 10:1 to 1:5, preferably from 5:1 to 1:4.
Here, when the content of component (A) based on the total amount of the resin composition is less than 10 wt %, the fluidity of the resin composition tends to be low, and the moldability of the resin composition in blow molding or extrusion molding is poor. On the other hand, if it exceeds 90 wt %, a gel or fish-eyes tend to increase. Further, in the weight ratio of component (B) and (C), when the amount of component (C) is too small, ESCR of the resin composition tends to be low, and when it is too much, the stiffness of the resin composition tends to be low.
The physical properties of the entire composition comprising components (A), (B) and (C), and constituted by the above-mentioned ratio, are such that the intrinsic viscosity [xcex7] is from 0.17 to 0.40 m3/kg, preferably from 0.18 to 0.35 m3/kg, and the density is from 935 to 968 kg/m3, preferably from 940 to 965 kg/m3.
When the intrinsic viscosity [xcex7] of the entire composition is less than 0.17 m3/kg, ESCR or the impact resistance tends to be low, and when it exceeds 0.40 m3/kg, the fluidity tends to be low, and the moldability tends to be poor. When the density of the composition is less than 935 kg/m3, the stiffness tends to be low, and when it exceeds 968 kg/m3, ESCR tends to be low.
The resin composition comprising ethylene-based polymers of the present invention comprises components (A), (B) and (C), as mentioned above, but it may contain various additives, as the case requires. Such additives may be ones commonly used for polyolefin compositions. For example, an antioxidant, an antistatic agent, an ultraviolet light absorber, a lubricant, a flame retardant or a compatibilizer may be mentioned.
The method for producing a resin composition comprising ethylene-based polymers of the present invention comprises carrying out three steps (a), (b) and (c), and these steps can be carried out in an optional order. At first, step (a) is carried out at a polymerization temperature within a range of from 70 to 100xc2x0 C. The reason for selecting the polymerization temperature to be from 70 to 100xc2x0 C. is that if it is less than 70xc2x0 C., the productivity becomes too low and if it exceeds 100xc2x0 C., a part of the polymer melts and forms an aggregated state, whereby continuous operation becomes difficult. In this step (a), by carrying out homopolymerization of ethylene or copolymerization of ethylene with an xcex1-olefin, an ethylene homopolymer or an ethylene copolymer having an xcex1-olefin content of from 0 to 0.5 wt %, preferably from 0 to 0.3 wt %, and an intrinsic viscosity [xcex7] of from 0.035 to 0.17 m3/kg, preferably from 0.040 to 0.15 m3/kg, is produced as component (A). At this time, the polymerization is carried out so that the amount of the polymer polymerized in this step becomes from 10 to 90 wt %, preferably from 30 to 80 wt % of the total composition. Here, the reason for limiting the xcex1-olefin content, the intrinsic viscosity [xcex7] and the amount of polymer, is the same as the reason for the limitation in the above-mentioned component (A).
Then, step (b) is carried out at a polymerization temperature within a range of from 40 to 90xc2x0 C. The reason for selecting the polymerization temperature to be from 40 to 90xc2x0 C. is that if it is less than 40xc2x0 C., the productivity becomes too low, and if it exceeds 90xc2x0 C., the productivity lowers and the intrinsic viscosity [xcex7] becomes difficult to control. Further, in this step (b), by performing homopolymerization of ethylene or copolymerization of ethylene with an xcex1-olefin, an ethylene homopolymer or an ethylene copolymer having an xcex1-olefin content of from 0 to 0.5 wt %, preferably from 0 to 0.3 wt %, and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg, preferably from 0.25 to 0.8 m3/kg, is produced as component (B). Here, the reason for limiting the xcex1-olefin content and the intrinsic viscosity [xcex7] is the same as the reason for the limitation in the above-mentioned component (B).
Further, step (c) is carried out at a polymerization temperature within a range of from 30 to 80xc2x0 C. The reason for selecting the polymerization temperature to be from 30 to 80xc2x0 C. is that if it is less than 30xc2x0 C., the productivity becomes too low, and if it exceeds 80xc2x0 C., the productivity becomes too low and the intrinsic viscosity [xcex7] become difficult to control. Further, in this step (c), by performing copolymerization of ethylene with an xcex1-olefin, an ethylene copolymer having an xcex1-olefin content of from 0.7 to 15 wt %, preferably from 1.0 to 13 wt %, and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg, preferably from 0.25 to 0.8 m3/kg, is produced as component (C). Here, the reason for limiting the xcex1-olefin content and the intrinsic viscosity [xcex7] is the same as the reason for the limitation in the above-mentioned component (C).
In the present invention, the molecular weights of components (B) and (C) are higher than that of component (A), as evident from intrinsic viscosities of each components, but they are not ultrahigh molecular weight as mentioned above. Further, the present invention has a characteristic that the difference in the molecular weight between component (B) and component (C) is not made so large, and the difference in the molecular weight between both components is preferably such that the difference in the intrinsic viscosity is preferably not more than 0.1 m 3/kg, particularly preferably not more than 0.05 m3/kg, and it is preferred to carry out the production so that the difference in the intrinsic viscosity become as small as possible. The reason is that if the difference in the molecular weight is high, the compatibility of the composition deteriorates and consequently, the composition becomes ununiform and gel, imperfections or fish-eyes are likely to form.
As mentioned above, in the process of the present invention, steps (a), (b) and (c) can be carried out in any optional order. However, normally, it is preferred to carry out the process in the order of step (a), step (b), followed by step (c), or in the order of step (b), step (a), followed by step (c).
In order to produce the copolymer of ethylene constituting the resin composition of the present invention, it is necessary to copolymerize an xcex1-olefin as a comonomer particularly to the high molecular weight portion. For this purpose, it is necessary to use a catalyst capable of providing good incorporation as much as possible, or to select an advantageous condition for copolymerization. As a catalyst for this purpose, a Ziegler type catalyst or a metallocene type catalyst may preferably be used. Particularly a Ziegler type catalyst or a metallocene type catalyst supported on a solid carrier is preferably used.
A Ziegler type catalyst to be used in the process of the present invention preferably consists of a solid catalyst component (E) containing at least titanium, magnesium and a halogen, and an organic aluminum compound component, as its main components. Here, the solid catalyst component (E) containing at least titanium, magnesium and a halogen, is preferably a composite solid formed by contacting a magnesium compound and a titanium halide compound. The method for its production and the obtained catalyst are not particularly restricted, and conventional ones can be used. As a specific method for producing the solid catalyst component (E), a method described, for example, in JP-B-50-32270, JP-B-52-13232 or JP-B-62-54326, may be used.
As the magnesium compound useful for producing the solid catalyst compound (E), various compounds used as carriers for Ziegler type catalysts may usually be used. For example, a magnesium halide such as magnesium chloride, magnesium bromide, magnesium iodide or magnesium fluoride, magnesium hydroxide, magnesium oxide, magnesium sulfate, magnesium carbonate, a hydroxymagnesium halide such as hydroxymagnesium chloride or hydroxymagnesium iodide, an alkoxy magnesium such as methoxy magnesium, ethoxy magnesium, propoxy magnesium or butoxy magnesium, an alkoxymagnesium halide such as methoxymagnesium chloride, methoxymagnesium bromide, ethoxymagnesium chloride, ethoxymagnesium bromide, propoxymagnesium chloride, propoxymagnesium bromide, butoxymagnesium chloride or butoxymagnesium bromide, an alkylmagnesium halide such as methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium bromide, propylmagnesium chloride, propylmagnesium bromide, butylmagnesium chloride or butylmagnesium bromide, or a mixture of these, may be mentioned.
Further, as the magnesium compound useful for producing the solid catalyst component (E), a reaction product (D) of an organic silicon compound shown hereinafter, with an organic magnesium compound, or a product produced by having the reaction product (D) further reacted with an aluminum alkoxide compound or an aluminum alkoxyhalide compound, may also be used. An example of a process for producing such magnesium compounds is disclosed in JP-B-52-13232 and JP-B-62-54326.
The organic silicon compound to be used for producing the above-mentioned reaction product (D) of the present invention is preferably a hydropolysiloxane compound having an optional degree of polymerization, represented by the following formula:
R1aHbSiO(4xe2x88x92axe2x88x92b)/2xe2x80x83xe2x80x83(I)
wherein R1 is a monovalent organic group selected from a group consisting of an alkyl group, an aryl group, an aralkyl group, an alkoxy group and an aryloxy group, and a is 0, 1 or 2, and b is 1, 2 or 3, provided a+bxe2x89xa63, or a mixture of such hydropolysiloxane compounds. With regard to its nature, various ones from liquid ones having low degrees of polymerization and a low viscosity to greasy or waxy ones having various degrees of polymerizations and a viscosity of up to 100 Pascalxc2x7second at 25xc2x0 C., and solid ones, may be mentioned. Since the structure of the terminal group of this hydropolysiloxane gives no substantial influence on the activity, it may be blocked by an optional inert group such as a trialkylsilyl group. As a specific example, tetramethyldisiloxane, diphenyldisiloxane, trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, methylhydropolysiloxane, phenylhydropolysiloxane, ethoxyhydropolysiloxane, cyclooctylhydropolysiloxane or chlorophenylhydropolysiloxane may be mentioned.
Another group of organic silicon compounds useful for producing the above-mentioned reaction product (D) of the present invention may be ones in which organic groups and hydroxyl groups are bonded to a silicon atom, particularly silane type compounds represented by the following formula:
R2nSi(OH)4xe2x88x92nxe2x80x83xe2x80x83(II)
wherein R2 is a monovalent hydrocarbon residue having from 1 to 18 carbon atoms, and n is a number of 1, 2 or 3, and if multiple R2 exist in one molecule, they may be the same or different, and polysiloxane type compounds which correspond to condensates thereof. As an example of R2 in formula (II), an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkaryl group may be mentioned. Such a group may be any one of straight chain type, branched chain type, saturated type, unsaturated type and ring type. As an example of the silane type compound of the above-mentioned formula (II) wherein n is 3, trimethylhydroxysilane, triethylhydroxysilane, triphenylhydroxysilane, methyldiphenylhydroxysilane or benzyldiphenylhydroxysilane, may be mentioned. Further, as an example of the compound wherein n is 2, diethyldihydroxysilane, dipropyldihydroxysilane, diallyldihydroxysilane, dicyclohexyldihydroxysilane or diphenyldihydroxysilane, may be mentioned. Further, as the compound wherein n is 1, butyltrihydroxysilane or phenyltrihydroxysilane, may be mentioned.
As the polysiloxane type compounds which correspond to condensates of the compounds of the above formula (II), ones having a siloxane condensation of Sixe2x80x94Oxe2x80x94Si and having a straight chain, a branched chain or a three-dimensional network structure, may be used. Their degrees of polymerization are not particularly limited, and they may cover from ones having low degrees of polymerization and a viscosity of several m pascalxc2x7sec (mPaxc2x7sec) at 25xc2x0 C., to greasy or waxy ones having a viscosity of up to 1,000,000 mPaxc2x7sec, and complete solid ones. As shown in formula (II), the polysiloxane type compound may be any one so long as it contains at least one hydroxyl group per molecule. However, one wherein the number of hydroxyl groups is too small, is not practically useful, and the content of hydroxyl groups in the polysiloxane type compound is preferably at least 0.1 wt %. As an example of such a polysiloxane type compound, an xcex1, xcfx89-dihydroxydimethylpolysiloxane represented by HO[Si(CH3)2O]nH (wherein, n is an integer of at least 2), or an xcex1, xcfx89-dihydroxymethylphenylpolysiloxane represented by HO[Si(CH3) (C6H5)O]nH (wherein, n is an integer of at least 2), may be mentioned.
As the organic magnesium compound to be used for the reaction with an organic silicon compound represented by the above formula (I) or (II), various types of organic magnesium compounds may be used. A preferred example may be a compound of the formula
(MgR32)pxc2x7(R3MgX)qxe2x80x83xe2x80x83(III)
(wherein R3 is a hydrocarbon group, X is a halogen atom, and p and q are numbers of from 0 to 1, having a relation of p+q=1) obtained by a reaction of a halogen-containing organic compound with metallic magnesium, its ether complex or a mixture thereof. As such an example, a so-called Gringnard reagent in a narrow sense represented by R3MgX i.e. p is 0 and q is 1, a dihydrocarbirmagnesium represented by R32Mg i.e. p is 1 and q is 0, other various organic magnesium halides represented by (MgR32)pxc2x7(R3MgX)q, an ether complex thereof or a mixture thereof, may be mentioned. These organic magnesium compounds may easily be prepared by conventional methods, for example, in an ether type solvent such as diethyl ether, dibutyl ether or tetrahydrofuran, or a hydrocarbon solvent such as heptane, octane, benzene or toluene, in the presence of an appropriate amount of a complexing agent such as an ether or an amine.
The method for reacting the organic silicon compound with the organic magnesium compound, may, for example, be the following method. Namely, for example, a Gringnard reagent prepared in a suitable solvent is added little by little to the organic silicon compound while stirring under an inert gas atmosphere. After all the amount is added, the stirring is continued for an additional predetermined period of time, to complete the reaction. The organic silicon compound can be used as it is without dilution. However, in some cases, it is more advantageous to use it as diluted by a hydrocarbon solvent or the like. This reaction can be carried out usually at a temperature of from xe2x88x9250xc2x0 C. to 100xc2x0 C. However, it is more advantageous to carry out the reaction at a temperature higher than room temperature. The reaction time in this case may sufficiently be from 30 minutes to 5 hours.
As the solvent for reaction, an inert hydrocarbon type solvent, namely, an aliphatic or aromatic hydrocarbon compound can be used. Specifically, hexane, heptane, cyclohexane, benzene, toluene or xylene may, for example, be mentioned. Further, an ether type solvent which is usually used for preparation of the above-mentioned Gringnard reagent, may also be used. The charging ratio of the organic silicon compound and the organic magnesium compound as raw materials, is preferably, OH:MgR3=1:0.05 to 1, in the case of an organic silicon compound having a hydroxyl group, as expressed by a molar ratio of hydroxyl groups in the organic silicon compound to the magnesium-hydrocarbon group bond (MgR3), and in the same way in the case of a hydropolysiloxane, it is preferably, Si:MgR3=1:0.05 to 1, as expressed by the molar ratio of silicon atoms (Si) in the hydropolysiloxane to the magnesium-hydrocarbon group bond (MgR3). And, it can be optionally selected from these ranges.
In the present invention, as mentioned above, a product or a solid component obtained by reacting the reaction product (D) with an aluminum alkoxide compound or an aluminum alkoxyhalide compound, can be used. A preferred aluminum compound which may be used at that time, is a compound represented by the following formula (IV):
Al(OR4)nX3xe2x88x92nxe2x80x83xe2x80x83(IV)
(wherein R4 is an alkyl group having from 1 to 12 carbons, n is in the range of 0 less than nxe2x89xa63, and X is an halogen atom.)
As a specific example, aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum mono-sec-butoxydiisopropoxide, aluminum tri-n-butoxide, aluminum tri-sec-butoxide, aluminum tri-t-butoxide, aluminum monoethoxydichloride, aluminum diethoxymonochloride, aluminum monoisopropoxydichloride or aluminum diisopropoxymonochloride may be mentioned.
The reaction of the reaction product (D) with the aluminum compound of the above formula (IV) is sufficiently achieved only by mixing or reacting them in an inert hydrocarbon solvent at a temperature within a range of from xe2x88x9210 to 150xc2x0 C. for from 5 minutes to 10 hours.
The halogen-containing titanium compound to be used for producing the Ziegler type solid catalyst component (E) of the present invention, is one represented by the formula TiXn(OR5)4xe2x88x92n (wherein X is a halogen atom, R5 is a hydrocarbon group having from 1 to 8 carbon atoms, and n is an integer from 1 to 4). A specific example may be titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichloro-n-butoxytitanium, dichlorodiethoxytitanium, dichlorodiisopropoxytitanium or dichlorodi-n-butoxytitanium. The Ziegler type solid catalyst component (E) of the present invention may contain vanadium besides titanium. A vanadium compound in this case may, for example, be vanadium tetrachloride, vanadyl trichloride, tetraethoxyvanadium, tetrabutoxyvanadium, triethoxyvanadium or tributoxyvanadium.
The reaction of the above-mentioned magnesium compound with the halogen-containing titanium compound, or with the halogen-containing titanium compound and the vanadium compound, is carried out usually preferably in an inert hydrocarbon solvent, at from 0 to 150xc2x0 C., preferably from 20 to 100xc2x0 C., for from 0.5 to 10 hours, preferably from 1 to 5 hours.
As the inert hydrocarbon solvent, an aromatic or halogenated aromatic hydrocarbon solvent such as benzene, toluene or chlorobenzene; or an aliphatic hydrocarbon solvent such as hexane, heptane or cyclohexane, may, for example, be used. After completion of the reaction, the solid phase is separated, and a free titanium or vanadium compound is removed by washing with an inert hydrocarbon solvent such as hexane, heptane or kerosine to recover the solid catalyst component (E).
The content of titanium, or titanium and vanadium, as transition metals in the solid catalyst component (E) thus obtained, can be appropriately adjusted by changing the condition for the reaction of the above-mentioned magnesium compound with the halogen-containing titanium compound, or with the halogen-containing titanium compound and the vanadium compound, such as the temperature, the time or the presence or absence of a solvent. Usually, the content is preferably from 1 to 120 mg as calculated as the transition metals per 1 g of the solid catalyst component (E). A catalyst using the solid catalyst component (E) having a content of the transition metals within this range, exhibits a high catalytic activity.
The metallocene catalyst as another catalyst preferably used in the present invention, is a catalyst which comprises a solid catalyst component (F) containing an aluminoxane and a metallocene compound, and an organic aluminum compound component, as the main components. Such a solid catalyst component (F) containing an aluminoxane and a metallocene compound, is a composite solid formed by contacting a solid carrier with an aluminoxane and a metallocene compound stepwise or all at once, and various known catalysts may be used without any particular restriction. For example, it can be obtained by reacting a solid carrier with an aluminoxane and a metallocene compound with stirring in a hydrocarbon solvent. A specific example of the method and the catalyst may be one disclosed in e.g. JP-A-8-208717, JP-A-10-255194 or JP-A-10-296535.
The solid carrier useful for the production of the solid catalyst compound (F) may, specifically, be an inorganic oxide such as silica, alumina, magnesia, zirconia or titania, a magnesium compound such as magnesium hydroxide, magnesium chloride or Mg(OH)Cl, a compound such as a chemically modified product of the above-mentioned reaction product (D), or an organic polymer such as polyethylene, polypropylene or polystyrene. Particularly, an inorganic oxide represented by silica or alumina, a magnesium compound represented by magnesium chloride or Mg(OH)Cl, or a chemically modified product of the above-mentioned reaction product (D), is preferably used.
As the solid carrier to be used in the present invention, a fine particulate solid having an average particle diameter within a range of from 1 to 500 xcexcm, preferably from 5 to 300 xcexcm, and having a specific surface area of from 5 to 1,000 m2/g, preferably from 50 to 800 m2/g, is preferred. One having a pore volume of from 0.3 to 3 cm3/g, preferably from 0.5 to 2.5 cm3/g, is preferred.
In the inorganic oxide or the magnesium compound as the solid carrier to be used in the present invention, the amount of water absorbed or the amount of hydroxyl groups on the surface varies depending on the treatment conditions. As their preferred ranges, the water content is at most 5 wt %, and the amount of hydroxyl groups on the surface is at least 1 pc/(nm)2 unit area. The water content and the amount of hydroxyl groups on the surface, can be controlled by selecting the calcination temperature or the calcination time. Usually, the calcination is carried out at a temperature of from 100 to 1,000xc2x0 C. for from 1 to 40 hours. Otherwise, instead of calcination, a chemical dehydration method using e.g. an organic aluminum compound, silicon tetrachloride or chlorosilane may be used.
As the chemically modified product of the reaction product (D), preferred is a fine particulate solid obtained by treating the reaction product (D) obtained by a reaction of the above-mentioned organic silicon compound with the organic magnesium compound, with an alcohol, followed by treating further with water, for example as disclosed in JP-A-10-255194.
As the aluminoxane to be used for producing the solid catalyst component (F), one commonly known, may be used. It may be prepared, for example, by a method of adding an aluminum compound little by little to a suspension in a hydrocarbon solvent containing a compound having absorbed water, such as silica, or a salt containing crystal water such as copper sulfate hydrate or copper aluminum sulfate hydrate, or a method of reacting an organic aluminum compound with water in a solid, liquid or gaseous phase in a hydrocarbon solvent.
As the metallocene compound to be used for the solid catalyst component (F), various known compounds may be used which have zirconium, titanium or hafnium as a metal centere, and which contain a ligand having e.g. a cyclopentadienyl skeleton or an indenyl skeleton, and contain a ligand X bonded to the transition metal. Here, the ligand X bonded to the transition metal may be optionally selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group and an aryloxy group wherein the hydrogen atom on the aromatic ring is substituted or not substituted.
As the above-mentioned metallocene compound, a group of compounds containing zirconium as the transition metal, and having a various aryloxy group such as a substituted or unsubstituted phenoxy group as the ligand X, may be mentioned.
Specifically, dicyclopentadienylbis(2-fluorophenoxy)zirconium, dicyclopentadienylbis(3-fluorophenoxy)zirconium, dicyclopentadienylbis(4-fluorophenoxy)zirconium, dicyclopentadienylbis(2-chlorophenoxy)zirconium, dicyclopentadienylbis(3-chlorophenoxy)zirconium, dicyclopentadienylbis(4-chlorophenoxy)zirconium, dicyclopentadienylbis(2-bromophenoxy)zirconium, dicyclopentadienylbis(3-bromophenoxy)zirconium, dicyclopentadienylbis(4-bromophenoxy)zirconium, dicyclopentadienylbis(2-iodophenoxy)zirconium, dicyclopentadienylbis(3-iodophenoxy)zirconium, dicyclopentadienylbis(4-iodophenoxy)zirconium, dicyclopentadienylbis(2,3-difluorophenoxy)zirconium, dicyclopentadienylbis(2,4-difluorophenoxy)zirconium, dicyclopentadienylbis(2,5-difluorophenoxy)zirconium, dicyclopentadienylbis(2,6-difluorophenoxy)zirconium, dicyclopentadienylbis(3,4-difluorophenoxy)zirconium, dicyclopentadienylbis(3,5-difluorophenoxy)zirconium, dicyclopentadienylbis(2,3-dichlorophenoxy)zirconium, dicyclopentadienylbis(2,4-dichlorophenoxy)zirconium, dicyclopentadienylbis(2,5-dichlorophenoxy)zirconium, dicyclopentadienylbis(2,6-dichlorophenoxy)zirconium, dicyclopentadienylbis(3,4-dichlorophenoxy)zirconium, dicyclopentadienylbis(3,5-dichlorophenoxy)zirconium, dicyclopentadienylbis(2,3,4-trifluorophenoxy)zirconium, dicyclopentadienylbis(2,3,5-trifluorophenoxy)zirconium, dicyclopentadienylbis(2,3,6-trifluorophenoxy)zirconium, dicyclopentadienylbis(2,4,5-trifluorophenoxy)zirconium, dicyclopentadienylbis(2,4,6-trifluorophenoxy)zirconium, dicyclopentadienylbis(3,4,5-trifluorophenoxy)zirconium, dicyclopentadienylbis(2,3,5,6-tetrafluorophenoxy)zirconium, dicyclopentadienylbis(pentafluorophenoxy)zirconium, dicyclopentadienylbis(2-fluoromethylphenoxy)zirconium, dicyclopentadienylbis(3-fluoromethylphenoxy)zirconium, dicyclopentadienylbis(4-fluoromethylphenoxy)zirconium, dicyclopentadienylbis(2-chloromethylphenoxy)zirconium, dicyclopentadienylbis(3-chloromethylphenoxy)zirconium, dicyclopentadienylbis(4-chloromethylphenoxy)zirconium, dicyclopentadienylbis(2-trifluoromethylphenoxy)zirconium, dicyclopentadienylbis(3-trifluoromethylphenoxy)zirconium, dicyclopentadienylbis(4-trifluoromethylphenoxy)zirconium, dicyclopentadienylbis(3,5-bistrifluoromethylphenoxy)zirconium, dicyclopentadienylbis(2-(2,2,2-trifluoroethyl)phenoxy)zirconium, dicyclopentadienylbis(3-(2,2,2-trifluoroethyl)phenoxy)zirconium, dicyclopentadienylbis(4-(2,2,2-trifluoroethyl)phenoxy)zirconium, dicyclopentadienylbis(2-trichloromethylphenoxy)zirconium, dicyclopentadienylbis(3-trichloromethylphenoxy)zirconium, dicyclopentadienylbis(4-trichloromethylphenoxy)zirconium, dicyclopentadienylbis(2-methylphenoxy)zirconium, dicyclopentadienylbis(3-methylphenoxy)zirconium, dicyclopentadienylbis(4-methylphenoxy)zirconium, dicyclopentadienylbis(2,3-dimethylphenoxy)zirconium, dicyclopentadienylbis(2,4-dimethylphenoxy)zirconium, dicyclopentadienylbis(2,5-dimethylphenoxy)zirconium, dicyclopentadienylbis(2,6-dimethylphenoxy)zirconium, dicyclopentadienylbis(3,4-dimethylphenoxy)zirconium, dicyclopentadienylbis(3,5-dimethylphenoxy)zirconium, dicyclopentadienylbis(2,3,4-trimethylphenoxy)zirconium, dicyclopentadienylbis(2,3,5-trimethylphenoxy)zirconium, dicyclopentadienylbis(2,3,6-trimethylphenoxy)zirconium, dicyclopentadienylbis(2,4,5-trimethylphenoxy)zirconium, dicyclopentadienylbis(2,4,6-trimethylphenoxy)zirconium, dicyclopentadienylbis(3,4,5-trimethylphenoxy)zirconium, dicyclopentadienylbis(pentamethylphenoxy)zirconium, dicyclopentadienylbis(2-methyl-4-fluorophenoxy)zirconium, dicyclopentadienylbis(2-chloro-4-fluorophenoxy)zirconium, dicyclopentadienylbis(2-chloro-4-trifluoromethylphenoxy)zirconium, dicyclopentadienylbis(2-fluoro-4-trifluoromethylphenoxy)zirconium, dicyclopentadienylbis(2-trifluoromethyl-4-fluorophenoxy)zirconium, dicyclopentadienylbis(2-ethylphenoxy)zirconium, dicyclopentadienylbis(3-ethylphenoxy)zirconium, dicyclopentadienylbis(4-ethylphenoxy)zirconium, dicyclopentadienylbis(2-isopropylphenoxy)zirconium, dicyclopentadienylbis(3-isopropylphenoxy)zirconium, dicyclopentadienylbis(4-isopropylphenoxy)zirconium, dicyclopentadienylbis(2-tertiarybutylphenoxy)zirconium, dicyclopentadienylbis(3-tertiarybutylphenoxy)zirconium, dicyclopentadienylbis(4-tertiarybutylphenoxy)zirconium, dicyclopentadienylbis(3,5-ditertiarybutylphenoxy)zirconium, dicyclopentadienylbis(2,8-dimethyl-1-naphtoxy)zirconium, dicyclopentadienylbis(1-tertiarybutyl-2-naphtoxy)zirconium, dicyclopentadienylbis(8-bromo-2-naphtoxy)zirconium, dicyclopentadienylbis(2-phenylphenoxy)zirconium, dicyclopentadienylbis(3-phenylphenoxy)zirconium, dicyclopentadienylbis(4-phenylphenoxy)zirconium, dicyclopentadienylbis(2-benzylphenoxy)zirconium, dicyclopentadienylbis(2-methoxycarbonylphenoxy)zirconium, dicyclopentadienylbis(2-acetoxyphenoxy)zirconium, dicyclopentadienylbis(2-cyanophenoxy)zirconium, dicyclopentadienylbis(2-nitrophenoxy)zirconium, dicyclopentadienylbis(2-dimethylaminophenoxy)zirconium, dicyclopentadienylbis(2-trifluoromethanesulfonylphenoxy)zirconium, dicyclopentadienylbis(4-fluorothiophenoxy)zirconium, dicyclopentadienylbis(2-trifluoromethylthiophenoxy)zirconium, dicyclopentadienylbis(3-trifluoromethylthiophenoxy)zirconium, bis(methylcyclopentadienyl)bis(2-chlorophenoxy)zirconium, bis(methylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium, bis(1,2-dimethylcyclopentadienyl)bis(2-ethylphenoxy)zirconium, bis(1,3-dimethylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium, bis(1,3-dimethylcyclopentadienyl)bis(3-tertiarybutylphenoxy)zirconium, bis(1,2,3-trimethylcyclopentadienyl)bis(2-fluorophenoxy)zirconium, bis(1,2,3-trimethylcyclopentadienyl)bis(3-fluorophenoxy)zirconium, bis(1,2,3-trimethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, bis(1,2,3-trimethylcyclopentadienyl)bis(2-isopropylphenoxy)zirconium, bis(1,2,4-trimethylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium, bis(1,2,4-trimethylcyclopentadienyl)bis(2-methylphenoxy)zirconium, bis(1,2,4-trimethylcyclopentadienyl)bis(3-methylphenoxy)zirconium, bis(1,2,4-trimethylcyclopentadienyl)bis(4-methylphenoxy)zirconium, bis(1,2,4-trimethylcyclopentadienyl)bis(2,4-dimethylphenoxy)zirconium, bis(1,2,4-trimethylcyclopentadienyl)bis(2,4-dichlorophenoxy)zirconium, bis(1,2,4-trimethylcyclopentadienyl)bis(2-tertiarybutylphenoxy)zirconium, bis(1,2,4-trimethylcyclopentadienyl)bis(3-tertiarybutylphenoxy)zirconium, bis(1,2,4-trimethylcyclopentadienyl)bis(4-tertiarybutylphenoxy)zirconium, bis(1,2,3,4-tetramethylcyclopentadienyl)bis(2-methoxyphenoxy)zirconium, bis(1,2,3,4-tetramethylcyclopentadienyl)bis(3-methoxyphenoxy)zirconium, bis(1,2,3,4-tetramethylcyclopentadienyl)bis(4-methoxyphenoxy)zirconium, bis(1,2,3,4-tetramethylcyclopentadienyl)bis(2-iodophenoxy)zirconium, bis(1,2,3,4-tetramethylcyclopentadienyl)bis(3-iodophenoxy)zirconium, bis(1,2,3,4-tetramethylcyclopentadienyl)bis(4-iodophenoxy)zirconium, bis(1,2,3,4-tetramethylcyclopentadienyl)bis(2-thiomethylphenoxy)zirconium, bis(1,2,3,4-tetramethylcyclopentadienyl)bis(3-thiomethylphenoxy)zirconium, bis(1,2,3,4-tetramethylcyclopentadienyl)bis(4-thiomethylphenoxy)zirconium, bis(pentamethylcyclopentadienyl)bis(2-fluorophenoxy)zirconium, bis(pentamethylcyclopentadienyl)bis(3-fluorophenoxy)zirconium, bis(pentamethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, bis(ethylcyclopentadienyl)bis(2-ethylphenoxy)zirconium, bis(ethylcyclopentadienyl)bis(3-ethylphenoxy)zirconium, bis(ethylcyclopentadienyl)bis(4-ethylphenoxy)zirconium, bis(isopropylcyclopentadienyl)bis(2-acetylphenoxy)zirconium, bis(isopropylcyclopentadienyl)bis(3-acetylphenoxy)zirconium, bis(isopropylcyclopentadienyl)bis(4-acetylphenoxy)zirconium, bis(isopropylcyclopentadienyl)bis(2-methylphenoxy)zirconium, bis(isopropylcyclopentadienyl)bis(3-methylphenoxy)zirconium, bis(isopropylcyclopentadienyl)bis(4-methylphenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(2-chlorophenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(3-chlorophenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(4-chlorophenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(3-trifluoromethylphenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(2-tertiarybutylphenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(3-tertiarybutylphenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(4-tertiarybutylphenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(2-cyanophenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(3-cyanophenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(4-cyanophenoxy)zirconium, bis(tertiarybutylcyclopentadienyl)bis(2-fluorophenoxy)zirconium, bis(tertiarybutylcyclopentadienyl)bis(3-fluorophenoxy)zirconium, bis(tertiarybutylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, bis(tertiarybutylcyclopentadienyl)bis(2-ethylphenoxy)zirconium, bis(tertiarybutylcyclopentadienyl)bis(3-ethylphenoxy)zirconium, bis(tertiarybutylcyclopentadienyl)bis(4-ethylphenoxy)zirconium, bis(tertiarybutylcyclopentadienyl)bis(2,4-dimethylphenoxy)zirconium, bis(1,3-ditertiarybutylcyclopentadienyl)bis(2-chlorophenoxy)zirconium, bis(1,3-ditertiarybutylcyclopentadienyl)bis(3-chlorophenoxy)zirconium, bis(1,3-ditertiarybutylcyclopentadienyl)bis(4-chlorophenoxy)zirconium, bis(1,3-ditertiarybutylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium, bis(1,3-ditertiarybutylcyclopentadienyl)bis(3-trifluoromethylphenoxy)zirconium, bis(1,3-ditertiarybutylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium, bis(phenylcyclopentadienyl)bis(2-phenylphenoxy)zirconium, bis(phenylcyclopentadienyl)bis(3-phenylphenoxy)zirconium, bis(phenylcyclopentadienyl)bis(4-phenylphenoxy)zirconium, bis(phenylcyclopentadienyl)bis(2,4-dichlorophenoxy)zirconium, bis(trimethylsilylcyclopentadienyl)bis(2-tertiarybutoxyphenoxy)zirconium, bis(trimethylsilylcyclopentadienyl)bis(3-tertiarybutoxyphenoxy)zirconium, bis(trimethylsilylcyclopentadienyl)bis(4-tertiarybutoxyphenoxy)zirconium, bis(trimethylsilylcyclopentadienyl)bis(2-phenylphenoxy)zirconium, bis(trimethylsilylcyclopentadienyl)bis(3-phenylphenoxy)zirconium, bis(trimethylsilylcyclopentadienyl)bis(4-phenylphenoxy)zirconium, bis(trimethylsilylcyclopentadienyl)bis(2,4-difluorophenoxy)zirconium, bis(cyclohexylcyclopentadienyl)bis(2-iodophenoxy)zirconium, bis(cyclohexylcyclopentadienyl)bis(3-iodophenoxy)zirconium, bis(cyclohexylcyclopentadienyl)bis(4-iodophenoxy)zirconium, bis(indenyl)bis(2-methylphenoxy)zirconium, bis(indenyl)bis(3-methylphenoxy)zirconium, bis(indenyl)bis(4-methylphenoxy)zirconium, bis(1-methylindenyl)bis(2-fluorophenoxy)zirconium, bis(1-methylindenyl)bis(3-fluorophenoxy)zirconium, bis(1-methylindenyl)bis(4-fluorophenoxy)zirconium, bis(2-methylindenyl)bis(2-bromophenoxy)zirconium, bis(2-methylindenyl)bis(3-bromophenoxy)zirconium, bis(2-methylindenyl)bis(4-bromophenoxy)zirconium, bis(5,6-dimethylindenyl)bis(2-isopropylphenoxy)zirconium, bis(5,6-dimethylindenyl)bis(3-isopropylphenoxy)zirconium, bis(5,6-dimethylindenyl)bis(4-isopropylphenoxy)zirconium, bis(5,6-dimethoxyindenyl)bis(2-cyanophenoxy)zirconium, bis(5,6-dimethoxyindenyl)bis(3-cyanophenoxy)zirconium, bis(5,6-dimethoxyindenyl)bis(4-cyanophenoxy)zirconium, bis(fluorenyl)bis(2-chlorophenoxy)zirconium, bis(fluorenyl)bis(3-chlorophenoxy)zirconium, bis(fluorenyl)bis(4-chlorophenoxy)zirconium, bis(4,5,6,7-tetrahydroindenyl)bis(2-tertiarybutylphenoxy)zirconium, bis(4,5,6,7-tetrahydroindenyl)bis(3-tertiarybutylphenoxy)zirconium, bis(4,5,6,7-tetrahydroindenyl)bis(4-tertiarybutylphenoxy)zirconium, bis(2-methyltetrahydroindenyl)bis(2-nitrophenoxy)zirconium, bis(2-methyltetrahydroindenyl)bis(3-nitrophenoxy)zirconium, bis(2-methyltetrahydroindenyl)bis(4-nitrophenoxy)zirconium, bis(2,7-ditertiarybutylfluorenyl)bis(2-trifluoromethylphenoxy)zirconium, bis(2,7-ditertiarybutylfluorenyl)bis(3-trifluoromethylphenoxy)zirconium, bis(2,7-ditertiarybutylfluorenyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(indenyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(indenyl)bis(4-fluorophenoxy)zirconium, ethylenebis(indenyl)bis(4-chlorophenoxy)zirconium, ethylenebis(indenyl)bis(2-fluorophenoxy)zirconium, ethylenebis(3-methylindenyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(3-methylindenyl)bis(4-fluorophenoxy)zirconium, ethylenebis(3-methylindenyl)bis(4-chlorophenoxy)zirconium, ethylenebis(3-methylindenyl)bis(2-fluorophenoxy)zirconium, ethylenebis(5,6-dimethylindenyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(5,6-dimethylindenyl)bis(4-fluorophenoxy)zirconium, ethylenebis(5,6-dimethylindenyl)bis(4-chlorophenoxy)zirconium, ethylenebis(5,6-dimethylindenyl)bis(2-fluorophenoxy)zirconium, ethylenebis(4,7-dimethylindenyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(4,7-dimethylindenyl)bis(4-fluorophenoxy)zirconium, ethylenebis(5,6-dimethoxyindenyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(5,6-dimethoxyindenyl)bis(4-fluorophenoxy)zirconium, ethylenebis(5,6-dihydroindenyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(5,6-dihydroindenyl)bis(4-fluorophenoxy)zirconium, ethylenebis(5,6-dihydroindenyl)bis(4-chlorophenoxy)zirconium, ethylenebis(5,6-dihydroindenyl)bis(2-fluorophenoxy)zirconium, ethylenebis(4,5,6,7-tetrahydroindenyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(4,5,6,7-tetrahydroindenyl)bis(4-fluorophenoxy)zirconium, ethylenebis(4,5,6,7-tetrahydroindenyl)bis(4-chlorophenoxy)zirconium, ethylenebis(4,5,6,7-tetrahydroindenyl)bis(2-fluorophenoxy)zirconium, methylenebis(cyclopentadienyl)bis(2-fluorophenoxy)zirconium, methylenebis(cyclopentadienyl)bis(2-ethylphenoxy)zirconium, methylenebis(methylcyclopentadienyl)bis(3-chlorophenoxy)zirconium, methylenebis(1,3-dimethylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium, methylenebis(n-butylcyclopentadienyl)bis(4-tertiarybutylphenoxy)zirconium, ethylenebis(3-methylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(3-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, ethylenebis(3-isopropylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(3-isopropylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, ethylenebis(3-tertiarybutylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(3-tertiarybutylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, isopropylidene(cyclopentadienyl)(indenyl)bis(4-trifluoromethylphenoxy)zirconium, isopropylidene(cyclopentadienyl)(indenyl)bis(4-fluorophenoxy)zirconium, isopropylidene(methylcyclopentadienyl)(indenyl)bis(4-trifluoromethylphenoxy)zirconium, isopropylidene(methylcyclopentadienyl)(indenyl)bis(4-fluorophenoxy)zirconium, isopropylidenebis(indenyl)bis(4-trifluoromethylphenoxy)zirconium, isopropylidenebis(indenyl)bis(4-fluorophenoxy)zirconium, isopropylidene(cyclopentadienyl)(fluorenyl)bis(4-trifluoromethylphenoxy)zirconium, isopropylidene(cyclopentadienyl)(fluorenyl)bis(4-fluorophenoxy)zirconium, isopropylidene(3-methylcyclopentadienyl)(fluorenyl)bis(4-trifluoromethylphenoxy)zirconium, isopropylidene(3-methylcyclopentadienyl)(fluorenyl)bis(4-fluorophenoxy)zirconium, tetramethylethylidenebis(2-tertiarybutylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium, tetramethylethylidenebis(2-tertiarybutylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(indenyl)bis(4-trifluoromethylphenoxy)zirconium, dimethylsilylenebis(indenyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(2-methylindenyl)bis(4-trifluoromethylphenoxy)zirconium, dimethylsilylenebis(2-methylindenyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(2-ethylindenyl)bis(4-trifluoromethylphenoxy)zirconium, dimethylsilylenebis(2-ethylindenyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(2-methyl-5-isopropylindenyl)bis(4-trifluoromethylphenoxy)zirconium, dimethylsilylenebis(2-methyl-5-isopropylindenyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)bis(4-trifluoromethylphenoxy)zirconium, dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(2-tertiarybutylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium, dimethylsilylenebis(2-tertiarybutylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(2-tertiarybutyl-4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(2-isopropyl-4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(2,3,5-trimethylcyclopentadienyl)(2,4,5-trimethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(2,4-dimethylcyclopentadienyl)(3,5-dimethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(3-tertiarybutylcyclopentadienyl)(4-tertiarybutylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(3-methylcyclopentadienyl)(4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(2,4-dimethylcyclopentadienyl)(3-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(2,4-dimethylcyclopentadienyl)(4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(3,4-dimethylcyclopentadienyl)(3-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(3-tertiarybutylcyclopentadienyl)(3-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(3-tertiarybutylcyclopentadienyl)(4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(2,3,5-trimethylcyclopentadienyl)(cyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(2,4-dimethylcyclopentadienyl)(cyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(3-tertiarybutylcyclopentadienyl)(cyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(3-methylcyclopentadienyl)(cyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(cyclopentadienyl)(indenyl)bis(4-trifluoromethylphenoxy)zirconium, dimethylsilylene(cyclopentadienyl)(indenyl)bis(4-fluorophenoxy)zirconium, diphenylsilylenebis(indenyl)bis(4-trifluoromethylphenoxy)zirconium, diphenylsilylenebis(indenyl)bis(4-fluorophenoxy)zirconium, dibenzylsilylenebis(indenyl)bis(4-trifluoromethylphenoxy)zirconium, dibenzylsilylenebis(indenyl)bis(4-fluorophenoxy)zirconium, methylphenylsilylenebis(2-methylindenyl)bis(4-trifluoromethylphenoxy)zirconium, methylphenylsilylenebis(2-methylindenyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(3,4-dimethylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium, dimethylsilylenebis(3,4-dimethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)bis(4-trifluoromethylphenoxy)zirconium or dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)bis(4-fluorophenoxy)zirconium, may, for example, be mentioned.
Further, in the present invention, besides the above listed metallocene compounds, metallocene compounds having, for example, a chlorine atom, a bromine atom, a hydrogen atom, a methyl group, an ethyl group, a benzyl group or a phenyl group, as the ligand X, may also be used. Specifically, bis(cyclopentadienyl) zirconium monochloride monohydride, bis(cyclopentadienyl)zirconium monobromide monohydride, bis(cyclopentadienyl)methylzirconium hydride, bis(cyclopentadienyl)ethylzirconium hydride, bis(cyclopentadienyl)phenylzirconium hydride, bis(cyclopentadienyl)benzylzirconium hydride, bis(cyclopentadienyl)neopentylzirconium hydride, bis(methylcyclopentadienyl)zirconium monochloride monohydride, bis(indenyl)zirconium monochloride monohydride, bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)zirconium dibromide, bis(cyclopentadienyl)methylzirconium monochloride, bis(cyclopentadienyl)ethylzirconium monochloride, bis(cyclopentadienyl)cyclohexylzirconium monochloride, bis(cyclopentadienyl)phenylzirconium monochloride, bis(cyclopentadienyl)benzylzirconium monochloride, bis(cyclopentadienyl)zirconium dichloride, bis(dimethylcyclopentadienyl)zirconium dichloride, bis(trimethylcyclopentadienyl)zirconium dichloride, bis(butylcyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)dimethylzirconium, bis(cyclopentadienyl)diphenylzirconium, bis(cyclopentadienyl)dibenzylzirconium, bis(indenyl) zirconium dichloride, bis(indenyl) zirconium dibromide, bis(fluorenyl)zirconium dichloride, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)diethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)methylzirconium monochloride, ethylenebis(indenyl)ethylzirconium monochloride, ethylenebis(indenyl)methylzirconium monobromide, ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dibromide, dimethylsilylenebis(cyclopentadienyl)zirconium dichloride, dimethylsilylenebis(indenyl)zirconium dichloride, dimethylsilylenebis(methylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(dimethylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(trimethylcyclopentadienyl)zirconium dichloride, isopropylidenebis(indenyl)zirconium dichloride or isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, may, for example, be mentioned.
Further, as the metallocene compound of the present invention, besides the above listed various compounds, metallocene compounds wherein the metal centere is changed from the zirconium atom to a titanium atom or a hafnium atom may also be used.
The method for preparing the solid catalyst component (F) of the present invention containing a metallocene compound and an aluminoxane, is not particularly restricted. For example, (1) a method of mixing the aluminoxane and a solid carrier, followed by supporting a catalytic reaction product of the metallocene compound with the aluminoxane, on the solid carrier, (2) a method of mixing the aluminoxane and the solid carrier, followed by contacting and supporting the metallocene compound thereon, (3) a method of supporting the metallocene compound on the solid carrier, followed by mixing with the aluminoxane, or (4) a method of contacting a reaction product of the metallocene compound with the aluminoxane, with the solid carrier, may be used.
The method of contacting and supporting the metallocene compound and/or the aluminoxane on the solid carrier, is usually carried out in an inert hydrocarbon solvent. As the inert hydrocarbon solvent in such a case, an aromatic hydrocarbon solvent such as benzene, toluene or xylene; an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, octane, decane or dodecane; or an alicyclic hydrocarbon solvent such as cyclopentane or cyclohexane, may, for example, be employed. Among them, an aromatic hydrocarbon solvent is particularly preferred.
The temperature for contacting the metallocene compound and/or the aluminoxane with the solid carrier, is usually from xe2x88x9250 to 200xc2x0 C., preferably from xe2x88x9220 to 100xc2x0 C., more preferably from 0 to 90xc2x0 C. Further, the contacting time is usually from 5 minutes to 100 hours, preferably from 10 minutes to 20 hours.
The ratio of the metallocene compound and the aluminoxane to be used in the present invention, is preferably such that the molar ratio of the metallocene compound/aluminum atoms in the aluminoxane, is from 1/1 to 1/1,000, preferably from 1/10 to 1/500.
The ratio of the solid carrier and the aluminoxane to be used in the present invention is preferably such that the ratio of mole of aluminum atoms in the aluminoxane/the solid carrier (g) is from 1/1 to 1/1,000, preferably from 1/10 to 1/500. Further, the ratio of the solid carrier and the metallocene compound is preferably such that the ratio of mole of the metallocene compound/the solid carrier (g) is from 1/5 to 1/10,000, preferably from 1/10 to 1/1,000.
The solid catalyst component (E) or the solid catalyst component (F) to be used in the present invention, may be pre-polymerized in the presence of an olefin. The method for such pre-polymerization is such that an xcex1-olefin is pre-polymerized in the presence of the solid catalyst component (E) or the solid catalyst component (F), if necessary in the presence of an organic aluminum compound.
The pre-polymerized solid catalyst component (E) or the pre-polymerized solid catalyst component (F) preferably contains the polymer in an amount of from 0.1 to 500 g, particularly from 0.3 to 300 g, per 1 g of the solid catalyst component (E) or the solid catalyst component (F).
In the present invention, ethylene is homo-polymerized, or ethylene and an xcex1-olefin having preferably at least 4 carbon atoms, particularly preferably from 4 to 20 carbon atoms, are copolymerized by a slurry polymerization method or a gas phase polymerization method in the presence of the solid catalyst component (E) or the solid catalyst component (F) subjected to or not subjected to the pre-polymerization as mentioned above. The xcex1-olefin may, for example, be 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene or 1-icocene. In the case of the slurry polymerization, the solvent for the polymerization may, for example, be an aliphatic hydrocarbon such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane or kerosine; an alicyclic hydrocarbon such as cyclopentane, cyclohexane or methylcyclopentane; an aromatic hydrocarbon such as benzene, toluene or xylene; or a halogenated hydrocarbon such as ethylene chloride, chlorobenzene or dichloromethane. These media may be used alone or in combination as a mixture.
The amount of the solid catalyst component used for the polymerization, is usually from 10xe2x88x928 to 10xe2x88x923 g atom, preferably from 10xe2x88x927 to 10xe2x88x924 g atom per 1 l of the polymerization volume, as calculated based on the transition metal atoms in the solid catalyst component (E) or the solid catalyst component (F). Further, the amount of the organic aluminum compound for polymerization is usually from 1 to 1,000 mole, preferably from 10 to 500 mole, per 1 g atom of the transition metal atoms in the solid catalyst component (E) or the solid catalyst component (F).
The slurry concentration in the slurry polymerization is usually within a range of at least 100 g/l, preferably from 100 to 700 g/l, more preferably from 150 to 600 g/l, particularly preferably from 200 to 500 g/l.
The total pressure in polymerization is usually from atmospheric pressure to 10 MPa, preferably from atmospheric pressure to 5 MPa. The polymerization can be carried out in any one of a batch process, a semi-continuous process and a continuous process. The molecular weight of the olefin polymer can be controlled by addition of hydrogen to the polymerization system or by changing the polymerization temperature.
Now, the present invention will be further described in more detail by way of Examples. However, the present invention is by no means restricted to such specific Examples.
The physical properties of resin composition in the present invention were measured by the following methods.
(1) xcex1-olefin content (unit: wt %)
Calculated by 13C-NMR measurement
(2) Intrinsic viscosity [xcex7] (unit: m3/kg)
Measured in accordance with JIS K7367-3 in a decalin solution of 135xc2x0 C.
(3) Density (unit: kg/m3)
Measured in accordance with JIS K7112 by a density-gradient column method (23xc2x0 C.).
(4) Flexural modulus (unit: MPa)
Measured in accordance with JIS K7171.
(5) ESCR (unit: h)
Measured in accordance with the polyethylene test method in the attachment (regulations) in JIS K6922-2.